sulphonic acib and carboxyhc acid



Patented Sept. 3, 1 935 rsr OFFICE STULPHONIC AGED AND CARBOXYLIC ACIDDERIVATIVE S 0F 1,1 -DHARYL-3,3' -ARYL ENE-5,5-B]IS-PYRAZLONES HerbertKracker and Richard Schmid, Frankfort-on-the-Main,

Germany, assignors to General Aniline Works, Inc., New York, N. Y., acorporation of Delaware No Drawing. Application March 9, 1934, SerialNo. 714,888. In Germany March 11, 1933' 4 Glaims.

The present invention relates to sulphonic acid and carboxylic acidderivatives of 1,1-diaryl-3,3- arylene-5,5-bis-pyraz01ones.

We have found that sulphonic acid and carboxylic acid derivatives of1,1'-cliaryl-3,3' arylene-5,5'-bis-pyrazolones of the formula:

1'2 R N It 00 N N oo R"OOC-CH2-CO-RCOCH2-COOR" with aromatic hydrazinesof the formula? RP-NI-L-NHZ wherein R and R have the above indicatedmeaning and R stands for an alkyl radical to form the bis-hydrazones andthen closing the bis-pyrazolone ring, likewise in water, thecorresponding alcohol being split off. The formation of the bishydrazoneand especially the ring-closure to the bis-pyrazolone occur withoutdifiiculty and with Very good yields.

As is known from the literature, pyrazolones without sulphonic andcarboxylic acid groups are easily obtainable by causing molecularproportions of an arylhydrazine to react upon acyl acetic esters. Thereaction velocity in these cases is so high that it is not possible toeliminate the hydrazone formed as intermediate product; there isdirectly formed the respective pyrazolone (of. H. Wieland, Die Hydrazine(1913), page 126).

If acyl acetic esters are caused to react with sulphonated orcarboxylated arylhydrazines the reaction velocity is much less. Thus itis possible, for instance, according to Berichte der deutschenchemischen Gesellschaft, vol. 25, (1892), page 1948, to condensepara-phenylhydrazine-sulphonic acid with aoetoacetic ester only with anexcess of the ester and even in this case only at temperatures of C.- C.The yield is extremely low, as the author himself states. Experimentshave shown that, when working in a solution of acetic acid of 50%strength, the yield is better but attains even then only 50% of thetheoretical. Furthermore, according to the statements in ChemischesZentralblatt, 1911, I, page 83, it is not at all possible to condensefree phenylhydrazine-para-sulphonic acid with furoyl acetic ester anding pyrazoione from the sodium salt of phenylhydrazine-para-sulphonicacid and the same ester takes place only at a temperature of C. and withlowest yield. It, therefore, was to be expected that the formation ofpyrazolones from arylhydrazine-sulphonic acids would be prevented bystearic or like hindrance, especially also in View of the observationswhich Rowe (cf. Chemisches Zentralblatt, 1921, III, page 331) madeduring his experiments to use arylhydrazine-ortho-sulphonic acids forcondensing reactions.

In View of the fact that the last named reac-- tions occur much moreslowly it is possible to eliminate the hydrazones from acyl aceticesters and sulphonated or carboxylated arylhydrazines, as will be seenfrom the examples of the present invention of the formation ofbis-hydrazones from aroylene-bis-aoetic esters and arylhydrazinescontaining sulphonicor carboXylic-acid groups. Only by further treatmentof these hydrazones, for instance, with alkalies at higher temperatures,the corresponding pyrazolones are formed.

A characteristic feature of the present process lies in the fact thatthenew Chemisches Zentralblatt 1911, 1, page 83. It-

had rather to be supposed that the reaction of sulphonated orcarboxylated arylhydrazines with aroylene-bis-acetic esters in anaqueous medium would not take place at all or only with bad yields,since according to Berend and Herms in Journal fiir praktische Chemie(2)74, page 125 et seq. the condensation of the water-insolthe formationof the correspondbis-pyrazolone derivatives are easily formed in anaqueous medium uble terephthaloyl-bis-acetic ester with phenylhydrazineto the corresponding 1,l-diphenyl- 3,3-(para-phenylene)5,5-bis-pyrazolone occurs only by heating the components in glacialacetic acid. Moreover, the use of an aqueous medium has the advantageover the reaction of acyl acetic esters containing heavy acyl radicalswith hydrazine derivatives containing sulphonic or carboxylic acidgroups, known according to literature, that the desired pyrazolonederivatives are obtained with very good yields.

The formation of the bis-hydrazones occurs with especial advantage inacid solution, the ring-closure to the bis-pyrazolone is advantageouslyconducted in a neutral or alkaline medium. The condensation to thebis-hydrazone and the subsequent ring-closure are preferably effected inthe same aqueous medium, without elimination of the bis-hydrazone.

The pyrazolones thus obtainable are valuable intermediate products forthe manufacture of dyestuffs.

The following examples serve to illustrate the invention, but they arenot intended to limit it thereto:

(1) 388 grams of 4hydroxy-3'-carboXy-4- sulpho 1,1diphenyl-sulphone-2hydrazine are suspended in 2500 cc. of water of 60 C. to 65 C. and thewhole is rendered weakly acid to Congo paper by means of sodiumcarbonate solution. Thereupon, 155 grams of terephthaloyl-bis-aceticethylester are quickly added and the whole is stirred for about aquarter of an hour at 60 C. to 65 C. The reaction hereby becomesstrongly acid to Congo paper. In the course of half an hour a solutionof grams of anhydrous sodium carbonate in water is slowly run in untilthe acid reaction to Congo has just disappeared. Now the reaction isstill very acid to litmus paper; the whole is entirely dissolved to abrown-yellow solution. After stirring for 2 hours at 65 C. to 70 (3.,free hydrazine can no longer be detected by means of Fehlings solution,that is to say, the formation of the bis-hydrazone is finished. 50 gramsof prepared chalk are then added and the mass is heated to from 83 C. to85 C. to effect the ring-closure. The temperature is maintained for 2 to3 hours, the whole is filtered by suction, while hot, and the hotsolution is run into a mixture'of 500 cc. of hydrochloric acid (specificgravity 1.163) and 300 grams of sodium chloride. The bis-pyrazoloneformed of the formula m-sulphophenylhydrazine 1,1 -di (3-sulphophenyl)-3,3- (para-phenylene) 5,5-bis-pyrazolone (grey-yellow powder)p-sulphophenylhydrazine l,1'di- (4"sulph0phenyl) 3,3 (para-phenylene)-5,5bis-pyrazolone (yellow powder) o-carboxyphenylhydrazine 1,1 di- (2"-carboxyphenyl) -3,3 (para-phenylene) -5,5-bis-pyrazo1one (yellowpowder) 2-chloro-4-sulphophenylhydrazine 1,1'di-(2" chloro l"sulphophenyl) 3,3- (para-phenylene) 5,5-bis-pyrazolone (yellowishgreypowder) 2-chloro-5su1phophenyl-hydrazine 1,l-di- (2 -chloro 5sulphophenyl) 3,3 (pphenylene) 5,5 bis pyrazolone (yellowishbrownpowder) 1-sulpho-2naphthyl-hydrazine l,l-di-(2-naphthyl- 1"su1ph0) 3,3-(p-phenylene) 5,5bis-pyrazolone (reddish-brown powder)3-carboXy-2hydroxy-5-sulph0phenyl-hydrazine 1,1-di- (3-carboxy-2"hydroxy 5" -sulphophenyl) -3,3 (p-phenylene) -5,5 -bis -pyrazolone(reddish-brown powder) i-sulpho-4=diphenyl-hydrazine 1,l-di-(="-diphenyl 4 sulpho) 3,3 (pphenylene)5,5-bis-pyrazolone (brownishpowder).

Instead of the terephthaloyl-bis-acetic ester there may also be used itssubstitution products. There may be obtained, for instance, fromchloroterephthaloyl-bis-acetic ester and m-sulphophenylhydrazine1,1-di-(3"-sulphophenyl) -3,3 (chloro-p-phenylene)-5,5-bis-pyrazolone(yellow powder); 2-chloro-4-sulphophenyl-hydrazine l,1-di- (2 chloro 4"sulphophenyl) 3,3- (chloro p phenylene) -5,5 bis pyrazolone (yellowpowder).

From nitroterephthaloyl-bis-acetic ester and p-carboxyphenylhydrazine1,1di-(4-carboxypheny1) -3,3'-(nitro-p-phenylene)-5,5-bis-pyrazolone(yellow powder); 1su1pho-2-naphthylhydrazine 1,1-di-(2-naphthyl-1-sulpho) 3,3 (nitrop-phenylene) -5,5bis-pyrazolone (reddish-yellowpowder) The yields of precipitated pyrazolone amount to about (2) 188grams of para-sulphophenylhydrazine are suspended in 1500 cc. of waterof 55 C.-60 C.

- soOsogn HOaS-OSOQOH coon /N\ /N\ coon precipitates with a grey colorand forms, after filtering with suction, washing and drying, a greypowder.

The yield of precipitated pyrazolone amounts to about 90% of thetheoretical.

By using in the above example instead of terephthaloyl-bis-aceticethyl-ester 143 grams of terephthaloyl-bis-acetic methyl-ester, the samepyrazolone is obtained.

In a similar manner there are obtained from: terephthaloyl-bis-aceticester and o-sulphophenylhydrazine 1,ldi- (2-sulphopheny1) -3,3'(para-phenylene) -5,5bispyrazolone (yellow powder) and rendered feeblyacid to Congo paper by means of sodium carbonate solution. grams ofisophthaloyl-bis-acetic ester are quickly added, whereupon the mass isstirred for half an hour. The reaction becomes again very acid to Congopaper. In the course of half an hour a solution of 50 grams of anhydroussodium carbonate in water is then run in, whereby the whole is entirelydissolved. The solution still shows a strongly acid reaction to litmuspaper. After stirring for 2 hours at 55 C.60 C. the formation ofhydrazone is finished and free hydrazine is no longer detectable.Thereupon, an aqueous solution of 50 grams of anhydrous sodium carbonateis added,

the whole is stirred for half an hour at 65 C.- 70 C. and heated to C.87C. This temperature is maintained for half an hour, the whole isfiltered and worked up as described in Example 1. The1,1-di-(4-sulphophenyl)-3,3'-(mphenylene)-5,5'-bis-pyrazolone of thefollowing formula:

is obtained in the form of a brownish-yellow crystalline powder with ayield of about 85% of the theoretical.

In a similar manner there are obtained from:

Isophthaloyl-bis-acetic ester and para-oarboxyphenylhydrazine 1,1-di- 1-carboXy-pheny1) 3,3 -i (m-phenylene) 5,5'-bispyrazolone (yellowishpowder);

Isophthaloyl-bis-acetic ester and Z-nethyllsulphophenylhydrazine1,1-di-(2"-methyl-4 sulpho phenyl) -3,3- (in-phenylene) -5,5' bispyrazolone (brownish powder);

Naphthoylene-1,4-bis-acetic ester and l-sulpho-2-naphthylhydrazine 1,1di (2" naphthyl 1" sulpho) 3,3 (1", i" naphthylene) 5,5 bis pyrazolone(brown-yellow powder) Naphthoylene-1,5-bis-acetic ester and3-carboxy-Z-hydroxy-fisulpho-phenylhydrazine l,1-di-(3-carboxy 2hydroXy-5-sulphophenyl) -3,3-(1,5" -naphthylene) -5,5-bis-pyrazolone(brown-yellow powder) Diphenyloyli/i-bis-acetic ester and 2-chloro-4-sulphophenylhydrazine 1,1 di (2 chloro 4 sulphophenyl)3,3-(4,4-diphenylene) -5,5 -bis -pyrazolone (yellow powder) (3) 233grams of 4-nitro-2-su1phonphenylhydrazine are suspended in 3000 cc. ofwater of 55 C.-60 C. and rendered feebly acid to Congo paper by means ofsodium carbonate solution. grams of terephthaloyl-bis-acetic ethyl-esterare quickly added and the mass is then stirred for half an hour. Thereaction becomes again very acid to Congo paper. In the course of halfan hour a solution of 60 grams of anhydrous sodium carbonate in water isrun in, until the reaction is no longer acid to Congo paper; thereaction is still very acid to litmus paper, the bis-hydrazone formedhas precipitated with a pure yellow color. The whole is stirred for 2hours at 60 C.-65 C. and again 50 grams of anhydrous sodium carbonatedissolved in water are added, whereby the reaction becomes distinctlyalkaline to brilliant yellow and dissolution begins. The whole isstirred for a further 1-2 hours at 60 C.65 C. and 168 cc. of causticsoda solution (specific gravity 1.383) are added, whereby a clearsolution is obtained. The temperature is raised to 65 C.-70 C., but nothigher, since otherwise decomposition accompanied by frothing takesplace. The whole is stirred for a quarter of an hour at the saidtemperature, cooled to 50 (3., filtered and the filtrate is run into 600cc. of hydrochloric acid (specific gravity 1.163)

and 600 grams of sodium chloride. Thereby, 1,1 di (4 nitro 2"sulphophenyl) 3,3 (para-phenylene)-5,5'-bis-pyrazolone of the followingformula:

02 OSOaH H033 precipitates with a brown-yellow color.

The yield of pyrazolone amounts to about 80% of thetheoretical. In asimilar manner there are obtained from Terephthaloyl-bis-acetic esterand. 2,5-disulphophenylhydrazine 1,1 di (2",5 disulphophenyl) 3,3 (pphenylene) -5,5-bis-pyrazolone (yellow powder) Isophthaloyl-bis-aceticester and 2-nitro-4- sulphophenylhydrazine 1,1 (11 (2" nitro 4sulphophenyl) 3,3-(m-phenylene) -5,5' -bis pyrazolone (brown powder)Chloroterephthaloyl bis acetic ester and 2-methyl-4,5disulphophenyl-hydrazine 1,1 di 2" methyl 4",5 disulphophenyl)3,3 (chloro p phenylene) 5,5 bis pyrazolone (yellow powder)Nitroterephthaloyl-bis-acetic ester and 4-mtro-2-sulpho-phenyl-hydrazine1,1 di (4 nitro 2" sulphophenyl) 3,3 (nitro-p-phenylene) 5,5 bispyrazolone (brown-yellow powder) Naphthoylene-1,5-bis-acetic ester and2-mitro-4-sulphophenylhydrazine 1,1 di 2" nitro 4 sulphophenyl) 3,3-(1"',5" naphthylene) -5,5bis -pyrazolone (brown powder)Diphenyloyl-4A-bis-acetic ester and 2,5-disulphophenylhydrazine 1,1 di(2,5" di sulphophenyl) 3,3 (4=",4""-diphenylene)-5,5-bis-pyrazolone(yel- 10w powder) In these cases too the yields are very good. Weclaim: 1. The compounds of the following general formula:

N N 00 \N N oo Hz( l -R( f l( lHa wherein R and R stand for radicals ofthe benzene, naphthalene or diphenyl series and wherein the radical Rcontains at least one substituent of the group consisting of sulphonicacid and carboxylic acid groups, representing well crystallized bodies,easily soluble in aqueous alkalies, capable of combining with diazocompounds.

2. The compound of the following formula:

representing a yellow crystallized body, easily soluble in aqueousalkalies, capable of combining with diazo compounds.

3. The compound of the following formula:

NO: I @SOaH H033 00 O representing a brown-yellow crystallized body,easily soluble in aqueous alkalies, capable of combining with diazocompounds.

4. The compound of the following formula:

Ho3s ooon 11000 $0311 OH HO 1% N

